Polymer complex coating agents, method for the production and use thereof

ABSTRACT

The invention relates to water-dilutable binding agents and coating agents with particularly quick drying surfaces. The invention also relates to a method for the production and use thereof. The water-dilutable binding agents are based on polymer dispersions, which are characterized in that they contain at least one poly acid/polyvinylpyrrolidone complex and optionally one or several water-soluble zircon compounds. The inventive binding agents have a quick drying surface and are suitable for use in the production of primers, paints and plasters with quick drying surfaces or quick-acting wash-fastness.

[0001] Coatings which dry rapidly at the surface are needed for manyapplications. The coated articles can be used almost immediately aftertheir coating and/or can be processed independently of weatherconditions, such as atmospheric humidity and temperature, for example.One typical example of such applications are roadmarking paints. Theyare intended to have very short drying times, so that the work can becarried out practically without closing the road. Other examples areexterior paints for the faces of buildings, the roofs of buildings,ships, and freight containers. In the case of these applications, thecoating must dry in an extremely short time or even during application,in order to be able to withstand the effects of weathering (such asrain, for example). Further fields of use are renders, which can be usedduring the transition from fall to winter, and also all kinds ofrelatively thick coatings which are applied to vertical masonryconstructions. Coatings of this kind are required to dry very rapidly sothat there is no unwanted running.

[0002] The conventional systems for rapid-drying coatings aresolventborne systems. With solvent-based paints it is possible tocontrol the rate of drying by varying the solids content and/or thesolvent.

[0003] Water-thinnable paints are environmentally friendly and in recenttimes have come more and more to displace their solvent-basedcounterparts. To prepare a coating composition on an aqueous basis,polymer dispersion binders are used.

[0004] A significant disadvantage of water-thinnable paints is thedependence of the drying rate on the atmospheric humidity. At lowatmospheric humidity said rate is often quick, in some cases evenquicker than with conventional paints. At high atmospheric humidities,however, such as in the morning and evening, and also before or afterrainfall, for example, the drying rate is very slow, since the waterevaporates very slowly.

[0005] For rapid-drying water-based coating compositions, there arethree different known principles possessing practical relevance:

[0006] 1) Flocculation principle:

[0007] a) Flocculation of the ionically stabilized binder followingapplication of the coating composition, which contains a polyamine andammonia as volatile base, by evaporation of the ammonia (U.S. Pat. No.5,527,853, EP-A-0 594 321, EP-A-0 728 822, EP-A-0 409 459).

[0008] b) Flocculation of the ionically stabilized binder by spraying anacid solution (WO 94/29 391) or a salt solution (EP-A-0 200 249, U.S.Pat. No. 4,571,415, U.S. Pat. No. 5,403,393) simultaneously with thecoating composition.

[0009] 2) Viscosity alteration at the surface of the coatingcomposition, by:

[0010] a) applying a thickener to the fresh coating, resulting in anincrease in viscosity (EP-A-0 721 003), or

[0011] b) applying a base to the fresh coating, containing a thickenerwhich, however, has not been activated by the setting of a low pH.

[0012] 3) Water absorption method:

[0013] In this case, substances which absorb water, such as silica gels,ion exchangers, and polymer gels, for example, are used during theapplication of the coating composition.

[0014] In the case of coating compositions where drying is activated byevaporation of a volatile base such as ammonia, the scope of applicationis limited (odor pollution etc.). Coating compositions which are broughtinto contact with salts following their application have thedisadvantage of being restricted to the use of weakly stabilizeddispersions. The salts used must be sprayed as a solution together withthe coating composition, or sprayed on or scattered on subsequently. Inthe case of subsequent application of the salts in solid or dissolvedform, considerable fractions may be washed away by rain, therebyseverely impairing the efficiency of the method. The quantities of saltwashed away by rain generally pass into the groundwater; consequently,this mode of drying is undesirable.

[0015] Surprisingly it has now been found that water-dilutable bindersbased on a polymer dispersion comprising at least onepolyacid/polyvinylpyrrolidone complex exhibit markedly accelerateddrying of the surface and a quicker wash resistance.

[0016] The overall concentration of polyacid/polyvinylpyrrolidonecomplexes in the binder is preferably less than 10% by weight, withparticular preference less than 5% by weight, and in particular lessthan 2% by weight.

[0017] The polyacids and the polyvinylpyrrolidones may in each casecomprise homopolymers or copolymers. It is possible to use all of thepolyacids that are known to the skilled worker. Preferred polyacids arepolyacrylic acids, polymethacrylic acids, and poly(co-methyl vinylether-maleic anhydrides). Particularly preferred polyacids are thepoly(co-methyl vinyl ether-maleic anhydrides). As polyacids it is alsopossible to use mixtures of polyacids.

[0018] As polyvinylpyrrolidones it is possible to use all of thepolyvinylpyrrolidones which are known to the skilled worker. Preferredpolyvinylpyrrolidones are poly(homo-N-vinylpyrrolidones) and copolymersof N-vinylpyrrolidone and esters of acrylic acid, methacrylic acidand/or maleic acid, which may also be used in the form of a colloiddispersion mixture, as disclosed, for example, in EP-A-0 894 809. Aspolyvinylpyrrolidones it is also possible to use mixtures ofpolyvinylpyrrolidones.

[0019] The polyacid/polyvinylpyrrolidone complexes are preferably 1:1complexes.

[0020] In order to improve the drying properties the binders of theinvention may where appropriate comprise not only thepolyacid/polyvinylpyrrolidone complexes but also one or morewater-soluble zirconium compounds, such as ammonium zirconium carbonate,zirconium acetoacetate, zirconium hydroxychloride, zirconiumorthosulfate, zirconium propionate and/or potassium zirconium phosphate,for example.

[0021] The binders contain preferably up to 50% by weight, withparticular preference from 0.5 to 10% by weight, and in particular from1 to 5% by weight of zirconium compounds, calculated as zirconium oxide.

[0022] Furthermore, the binders of the invention may where appropriatefurther comprise salts, acids, bases, low molecular mass organicsubstances, film formers, dispersants, protective colloids, stabilizers,surfactants, emulsifiers, polymers, thickeners, wetting agents,pigments, fillers, preservatives and/or defoamers.

[0023] Advantageously, no special requirements are imposed on thepolymer dispersions present in the binders. Thus it is also possible touse relatively stable polymer dispersions, such asprotective-colloid-stabilized dispersions, for example. Similarly, thebinders need not necessarily be adjusted to a high pH.

[0024] The polymer dispersions may be based on homopolymers and/orcopolymers and may where appropriate further comprise additives andauxiliaries. The polymer dispersions may be prepared by all of thetechniques known to the skilled worker, such as emulsion polymerization,for example.

[0025] In one preferred embodiment the copolymers contain from 70 to99.7% by weight, based on the total amount of the monomers, of monomersfrom the group of alkenes, such as ethene, propene or butene, dienes,such as butadiene or isoprene, acrylates and methacrylates of (C₁-C₁₂)monoalcohols, preferably of (C₁-C₈) monoalcohols, examples beingmethanol, ethanol, isopropanol, isobutanol, n-butanol and 2-ethylhexylalcohol, vinylaromatic monomers, vinyl esters of (C₁-C₁₂)alkanemonocarboxylic acids, examples being vinyl acetate, vinylpropionate, vinyl n-butyrate, vinyl laurate, ®VeoVa 9 and ®VeoVa 10(Shell-Chemie, vinyl esters of α,α-dialkyl-branched monocarboxylicacids), vinyl halides, examples being vinyl chloride and vinylidenechloride, α,β-monoolefinically unsaturated nitrites, examples beingacrylonitrile and methacrylonitrile, and alkyl esters ofmonoolefinically unsaturated dicarboxylic acids, examples beingdi-n-butyl maleate and fumarate.

[0026] The copolymers further preferably contain from 0.3 to 10% byweight, with particular preference from 0.5 to 5% by weight, based onthe total amount of the monomers, of α,β-monoolefinically unsaturatedmonocarboxylic and dicarboxylic acids, such as acrylic acid, methacrylicacid, itaconic acid, maleic acid, and fumaric acid, for example, andamides with or without substitution on the nitrogen atoms, such asacrylamide, methacrylamide, N-methylolacrylamide, andN-butoxy-methacrylamide, for example.

[0027] Additionally, the copolymers may contain from 0 to 20% by weight,preferably from 0.5 to 5% by weight, based on the total amount of themonomers, of functional monomers, such as hydroxyl-containing monomers,for example, such as hydroxyalkyl acrylates and methacrylates,especially hydroxyethyl methacrylate and hydroxypropyl methacrylate,and/or acetylacetoxy-containing monomers which improve the wet adhesion,especially allyl acetoacetate, acetylacetoxyethyl methacrylate, andacetylacetoxybutyl methacrylate, and/or monomers with a crosslinkingaction, such as monomers containing epoxide groups and monomerscontaining silane groups, especially glycidyl acrylate, glycidylmethacrylate, vinyltrimethoxysilane, andmethacryloyloxypropyltrimethoxysilane, and/or nitrogen-containingmonomers from the group of polymerizable monomers containing an amino,ureido or N-heterocyclic group, examples being dimethylaminoethylacrylate and methacrylate, N-(2-methacryloylethyl)ethyleneurea, and/ormonomers containing keto groups, examples being diacetoneacrylamide,diacetone-methacrylamide, acrolein, and 2-butanone methacrylate.

[0028] In self-crosslinking dispersions polymers containing keto groupsmay further contain up to 5% by weight, based on the total amount of themonomers, of a difunctional or polyfunctional carboxylic hydrazide, anexample being adipic hydrazide.

[0029] For the preparation of the binders of the invention, at least onepolyacid/polyvinylpyrrolidone complex is added to a polymer dispersion,which may also contain additives and/or auxiliaries, and then, whereappropriate, one or more water-soluble zirconium compounds, salts,acids, bases, low molecular mass organic substances, film formers,dispersants, protective colloids, stabilizers, surfactants, emulsifiers,polymers, thickeners, wetting agents, pigments, fillers, preservativesand/or defoamers are added to the polymer dispersion/complex mixture.

[0030] The binders of the invention are suitable as binders forwater-thinnable coating compositions in the widest sense.

[0031] The present invention accordingly further provideswater-thinnable coating compositions which comprise the binders of theinvention and which as a result exhibit accelerated drying of thesurface and a quicker wash resistance.

[0032] With preference, the coating compositions of the inventioncomprise primers, exterior paints, interior paints, coating materials,exterior renders, interior renders, or coating compositions for masonryconstructions in the widest sense.

[0033] The coating compositions of the invention are particularlysuitable as road marking paints.

[0034] A process for preparing the coating compositions of the inventionmay comprise adding the necessary additives and/or auxiliaries, such aspigments, fillers, film formers, dispersants, protective colloids,stabilizers, surfactants, emulsifiers, polymers, thickeners, wettingagents, preservatives and/or defoamers, for example, to a binder of theinvention.

[0035] A further process for preparing the coating compositions of theinvention may comprise adding at least one binder of the invention to awater-thinnable coating composition.

[0036] Finally, the coating compositions of the invention may also beprepared by adding at least one polyacid/polyvinylpyrrolidone complexand, where appropriate, one or more water-soluble zirconium compounds toa water-thinnable coating composition.

[0037] The invention also provides for the use ofpolyacid/polyvinylpyrrolidone complexes and mixtures comprising at leastone polyacid/polyvinylpyrrolidone complex and, where appropriate, one ormore water-soluble zirconium compounds in water-thinnable binders andcoating compositions and, in particular, for their use as dryingaccelerators.

[0038] The examples which follow are intended to illustrate theinvention without, however, restricting it.

[0039] In the examples below,

[0040] a) polyacid/polyvinylpyrrolidone complexes are prepared,

[0041] b) the drying times of binders with and withoutpolyacid/polyvinylpyrrolidone complex are measured,

[0042] c) masonry paints with and without polyacid/polyvinylpyrrolidonecomplex are prepared and their wash resistances are measured,

[0043] d) interior paints with and without polyacid/polyvinylpyrrolidonecomplex are prepared and their wash resistances are measured, and

[0044] e) synthetic resin renders with and withoutpolyacid/polyvinylpyrrolidone complex and synthetic resin renders withand without polyacid/polyvinylpyrrolidone complex and also zirconiumcompound are prepared and their wash resistances are measured.

[0045] a) Preparation of Polyacid/Polyvinylpyrrolidone Complexes:

EXAMPLE 1 Preparation of a 1:1 Poly(co-methyl Vinyl Ether-maleicAnhydride)/Poly(homovinylpyrrolidone) Complex

[0046] For this purpose, equal amounts of a 10% strength poly(co-methylvinyl ether-maleic anhydride) solution (Gantrez® AN 169 from ISP Global)and a 10% strength polyvinylpyrrolidone K-90 solution (from ISP Global)are mixed thoroughly with one another with careful stirring. Thisproduces a highly viscous, whitish yellow mixture whose pH is adjustedto about 7.5 using concentrated ammonia.

EXAMPLE 2 Preparation of a 1:1 Poly(co-methyl Vinyl Ether-maleicAnhydride)/Poly(co-vinylpyrrolidone-acrylate) Complex

[0047] For this purpose, equal amounts of a 10% strength poly(co-methylvinyl ether-maleic anhydride) solution (Gantrez® AN 169 from ISP Global)and a 10% strength poly(co-vinylpyrrolidone-acrylate) solution(Mowiplus® SA 575 from Clariant) are mixed thoroughly with one anotherwith careful stirring. This produces a highly viscous, whitish yellowmixture whose pH is adjusted to about 7.5 using concentrated ammonia.

[0048] b) Measuring the Drying Times of Binders with and withoutPolyacid/Polyvinylpyrrolidone Complex:

[0049] Binders used are the four polymer dispersions A, B, C, and D, andtheir mixtures with polyacid/polyvinylpyrrolidone complexes. Themixtures of the polymer dispersions with thepolyacid/polyvinylpyrrolidone complexes are referred to below as polymerdispersion/complex mixtures.

[0050] Polymer Dispersions A, B, C, and D:

[0051] Dispersion A (Mowilith® DM 2452 from Clariant): aqueous,plasticizer-free dispersion (approximately 50%) of vinyl acetate,Versatic acid vinyl ester, and an acrylate. The dispersion is stabilizedwith surface-active substances.

[0052] Dispersion B (Mowilith® LDM 1871 from Clariant): aqueous,plasticizer-free dispersion (approximately 53%) of vinyl acetate andethylene. The dispersion is stabilized with surface-active substancesand highly polymeric compounds.

[0053] Dispersion C (Mowilith® DM 777 from Clariant): aqueous,plasticizer-free dispersion (approximately 46%) based on acrylates andmethacrylates. The dispersion is stabilized with surface-activesubstances.

[0054] Dispersion D (Mowilith® LDM 6636 from Clariant): aqueous,plasticizer-free dispersion (approximately 50%) based on acrylates andstyrene. The dispersion is stabilized with surface-active substances.

[0055] Preparing the Polymer Dispersion/Complex Mixtures:

[0056] For preparing the polymer dispersion/complex mixtures the polymerdispersions A to D are mixed thoroughly with thepolyacid/polyvinylpyrrolidone complex from example 1, with stirring. Theamount of complex in the mixture is 1% by weight based on the solidscontent of the mixture.

[0057] Measuring the Drying Times of the Polymer Dispersions and of thePolymer Dispersion/Complex Mixtures:

[0058] In examples 3 to 6, following an aging time of 1 day, dispersionsA to D and dispersions A to D containing thepolyacid/polyvinylpyrrolidone complex from example 1 are drawn down ontoa glass plate using a 300 μm-gap doctor blade. Following drawn down, adrop of water is applied to the films immediately. On the basis of theclouding of the drop, an assessment is made as to whether skin formationor drying of the films takes place. Following application of the firstdrop, a further drop is placed on the films every 5 minutes and theclouding of the drop is assessed. The point in time at which clouding ofthe drop is no longer observed indicates the drying time of thedispersion films. Table 1 lists the drying times, thus determined, ofthe dispersion films A to D and the drying times of the dispersion filmsA to D containing the polyacid/polyvinylpyrrolidone complex fromexample 1. TABLE 1 Drying times of the polymer dispersions A to D and ofthe corresponding polymer dispersion/complex mixtures at roomtemperature without complex, with complex, Example Dispersion dryingtime in minutes drying time in minutes 3 A 20 0 4 B 5 0 5 C 25 0 6 D 250

[0059] It can be seen that the drying times of all dispersions aredrastically shortened by adding a polyacid/polyvinylpyrrolidone complex.

[0060] c) Preparing Masonry Paints with and withoutPolyacid/Polyvinylpyrrolidone Complex and Measuring their WashResistance:

[0061] Table 2 shows the formulation of the masonry paints prepared inexamples 7 to 13. The binders used are the polymer dispersions A to Dand mixtures thereof with the polyacid/polyvinylpyrrolidone complexesfrom examples 1 and 2 respectively. The polymer dispersion/complexmixtures always contain 1% by weight of complexes. The masonry paintsare prepared by mixing the constituents indicated in table 2. TABLE 2Formulation of the masonry paints of examples 7 to 13 Constituents Partsby weight Water 130.0 Mowiplus ® XW 330 (Clariant) 3.0 Tylose ® MH 4000KG 4 (Clariant) 2.0 Calgon ® N, 10% (BK Guilini) 11.0 Defoamer Agitan ®232 (Münzing Chemie GmbH) 4.0 Titanium dioxide Kronos ® 2065 (Kronos)226.0 Omyacarb ® 5 GU (Omyacarb) 168.0 Micro Talc ® AT 1 (Norwegian)38.0 China Clay ® B (ECCI) 20.0 Preservative Mergal ® K 10 N (Troy AG)2.0 Binder 375.0 Ammonia conc. (25% strength) (Riedel de Haen) 2.0 Whitespirit (ESSO Becker) 11.0 Butyl diglycol acetate (Merck-Schuchardt) 8.01000.0

[0062] Determining the Wash Resistances of the Masonry Paints:

[0063] For determining the wash resistances of the masonry paints ofexamples 7 to 13 they are drawn down onto a glass plate (6 cm×16 cm)using a 100 μm-gap or 300 μm-gap doctor blade. After different times(stopwatch) the glass plates are placed in a glass beaker and 100 g ofDI water are run over them evenly. Subsequently, using a photometer, thetransmittance (%) of the runoff water is measured. Here it is the casethat, with increasing drying of the paint films, the transmittance ofthe runoff water increases. A transmittance of 100% denotes completedrying of the film.

EXAMPLE 7 Wash Resistances of Masonry Paints (Wet Film Thickness 300 μm)at Room Temperature, Containing as Binders the Dispersion A, with andwithout Complex from Example 1

[0064] Time Transmittance without Transmittance with (minutes) complex(%) complex (%) 2 0.5 4 5 0.5 16 7 0.5 18 10 0.5 46 15 0.8 51 25 2 77 3034 94 35 60 100 40 82 100 45 100 100

EXAMPLE 8 Wash Resistances of Masonry Paints (Wet Film Thickness 100 μm)at Room Temperature, Containing as Binders the Dispersion B, with andwithout Complex from Example 1

[0065] Time Transmittance without Transmittance with (minutes) complex(%) complex (%) 2 11 89 5 21 94 7 22 96 10 81 100 15 100 100

EXAMPLE 9 Wash Resistances of Masonry Paints (Wet Film Thickness 300 μm)at Room Temperature, Containing as Binders the Dispersion C, with andwithout Complex from Example 1

[0066] Time Transmittance without Transmittance with (minutes) complex(%) complex (%) 2 0.5 2 5 0.5 5 7 0.7 35 10 0.8 44 15 3 55 20 4 60 25 670 35 87 90 40 95 100 45 100 100

EXAMPLE 10 Wash Resistances of Masonry Paints (Wet Film Thickness 100μm) at Room Temperature, Containing as Binders the Dispersion D, withand without Complex from Example 1

[0067] Time Transmittance without Transmittance with (minutes) complex(%) complex (%) 2 1 36 5 3 70 7 98 85 10 100 100 15 100 100

EXAMPLE 11 Wash Resistances of Masonry Paints (Wet Film Thickness 100μm) at +5° C., Containing as Binders the Dispersion B, with and withoutComplex from Example 1

[0068] Time Transmittance without Transmittance with (minutes) complex(%) complex (%) 5 2 62 7 3 74 10 4 90 15 37 95 20 75 99 25 99 99

EXAMPLE 12 Wash Resistances of Masonry Paints (Wet Film Thickness 100μm) at +5° C., Containing as Binders the Dispersion C, with and withoutComplex from Example 1

[0069] Time Transmittance without Transmittance with (minutes) complex(%) complex (%) 5 2 48 7 3 60 10 7 67 15 31 82 20 52 92 25 99 99

EXAMPLE 13 Wash Resistances of Masonry Paints (Wet Film Thickness 300μm) at +5° C., Containing as Binders the Dispersion C, with and withoutComplex from Example 2

[0070] Time Transmittance without Transmittance with (minutes) complex(%) complex (%) 5 1 2 10 2 5 15 3 33 25 5 55 30 5 70 40 38 83 50 99 94

[0071] It can be seen that the wash resistances of the masonry paintsare increased in all examples by adding a polyacid/polyvinylpyrrolidonecomplex.

[0072] d) Preparing Interior Paints with and withoutPolyacid/Polyvinylpyrrolidone Complex and Measuring their WashResistances:

[0073] Table 3 shows the formulation of the interior paints prepared inexample 14. The binders used are polymer dispersion C or a mixturethereof with the polyacid/polyvinylpyrrolidone complex from example 1.The polymer dispersion/complex mixture contains 1% by weight of complex.The interior paints are prepared by mixing the constituents indicated intable 3. TABLE 3 Formulation of the interior paints of example 14Constituents Parts by weight Water 310 Tylose ® MHB 10000 yp (Clariant)3.5 Calgon ® N (10% aqueous sol.) (BK Guilini) 15 Additol ® XW 330(Clariant) 2 Agitan ® 217 (Münzing Chemie GmbH) 1 Mergal ® AF (Troy AG)2 Ammonia (Riedel de Haen) 0.5 Titanium dioxide Kronos ® 2065 (Kronos)70 Talc AT 1 40 Socal ® P 2 (Deutsche Solvay-Werke GmbH) 100 ChinaClay ® B (ECCI) 40 Omyacarb ® 2 GU (Omyacarb) 150 Omyacarb ® 5 GU(Omyacarb) 150 Binder 100 White spirit ® (ESSO Becker) 10 Butyl diglycolacetate (Merck-Schuchardt) 6 1000.0

[0074] Measuring the Wash Resistances of the Interior Paints:

[0075] The wash resistances of the interior paints from example 14 aremeasured in the same way as the wash resistances of the masonry paintsof examples 7 to 13.

EXAMPLE 14 Wash Resistances of Interior Paints (Wet Film Thickness 100μm) at Room Temperature, Containing as Binders the Dispersion C, withand without Complex from Example 1

[0076] Transmittance Time without complex Transmittance with complex(minutes) (%) (%) 2 3 13 5 7 25 7 15 63 10 26 96 15 100 100

[0077] It can be seen that the wash resistance of the interior paint isincreased by adding a polyacid/polyvinylpyrrolidone complex.

[0078] e) Preparing Renders with and withoutPolyacid/Polyvinylpyrrolidone Complex and also Renders with and withoutPolyacid/Polyvinylpyrrolidone Complex and Zirconium Compound, andMeasuring their Wash Resistances

[0079] Table 4 shows the formulation of the synthetic resin rendersprepared in examples 15 and 16. In example 15 the polymer dispersion Aor a mixture thereof with the polyacid/polyvinylpyrrolidone complex fromexample 1 is used. In example 16 the polymer dispersion A or a mixturethereof with the polyacid/polyvinylpyrrolidone complex from example 1and a zirconium compound (Bozefix® PAS 5200 from Clariant) is used. Theconcentration of the polyacid/polyvinylpyrrolidone complex in the binderis 1% by weight, that of the zirconium compound 2% by weight. TABLE 4Formulation of the synthetic resin renders of examples 15 and 16Constituents Parts by weight Water 51.5 Tylose ® MH 10000 YP 2(Clariant) 1.5 Mowiplus ® XW 330 (Clariant) 3.0 Mergal ® K 10 N (TroyAG) 2.0 Calgon ® N, 10% (BK Guilini) 6.0 Sodium hydroxide solution, 10%(Riedel de Haen) 2.0 Agitan ® 218 (Münzing Chemie GmbH) 2.0 Binder 140.0Titanium dioxide Kronos ® 2160 (Kronos) 20.0 China Clay ® B (ECCI) 20.0Omyacarb ® GU (Omyacarb) 150.0 Omyacarb ® 130 GU (Omyacarb) 170.0Calcilit ® 0.1-0.5 (Omyacarb) 100.0 Calcilit ® 1.5-2.0 (Omyacarb) 300.0White spirit (ESSO Becker) 4.0 Butyl diglycol acetate (Merck-Schuchardt)6.0 Polyethylene FPE 930 T (Schwarzwälder Textilwerke 2.0 HeinrichKaulsmann GmbH) 980.0

[0080] Measuring the Wash Resistances of the Synthetic Resin Renders:

[0081] The wash resistances of the synthetic resin renders from examples15 and 16 are measured in the same way as the wash resistances of themasonry paints from examples 7 to 13. Etherplan boards were used as thesubstrate. The coat thickness of the renders is 3 mm.

EXAMPLE 15 Wash Resistances of Synthetic Resin Renders (Coat Thickness 3μm) at Room Temperature, Containing as Binder the Dispersion A, with andwithout Complex from Example 1

[0082] Transmittance Time without complex Transmittance with complex(minutes) (%) (%) 60 10 27 75 43 65 90 45 68

EXAMPLE 16 Wash Resistances of Synthetic Resin Renders (Coat Thickness 3Elm) at Room Temperature, Containing as Binder the Dispersion A or aMixture of Dispersion A and the Complex from Example 1 and a ZirconiumCompound (Bozefix® PAS 5200 from Clariant)

[0083] Transmittance without Transmittance with (complex + (complex +Time zirconium compound) zirconium compound) (minutes) (%) (%) 60 9 3075 42 68 90 44 72 120 55 80 150 60 91

[0084] It can be seen that the wash resistances of the synthetic resinrenders are increased by adding a polyacid/polyvinylpyrrolidone complexand, respectively, by adding a polyacid/polyvinylpyrrolidone complex anda zirconium compound.

1. A water-thinnable binder based on a polymer dispersion prepared byemulsion polymerization, characterized in that it comprises at least onepolyacid/polyvinylpyrrolidone complex.
 2. The binder of claim 1,characterized in that the overall concentration ofpolyacid/polyvinylpyrrolidone complexes in the binder is less than 10%by weight.
 3. The binder of claim 1 or 2, characterized in thatpolyacids used comprise polyacrylic acids, polymethacrylic acids and/orpoly(co-methyl vinyl ether-maleic anhydrides).
 4. The binder of at leastone of claims 1 to 3, characterized in that polyvinylpyrrolidones usedcomprise poly(homo-N-vinylpyrrolidones) and/or copolymers ofN-vinylpyrrolidone and esters of acrylic acid, methacrylic acid and/ormaleic acid.
 5. The binder of at least one of claims 1 to 4,characterized in that the polyacid/polyvinylpyrrolidone complexes are1:1 complexes.
 6. The binder of at least one of claims 1 to 5,characterized in that the binder further comprises one or morewater-soluble zirconium compounds.
 7. The binder of at least one ofclaims 1 to 6, characterized in that the binder further comprises salts,acids, bases, low molecular mass organic substances, film formers,dispersants, protective colloids, stabilizers, surfactants, emulsifiers,polymers, thickeners, wetting agents, pigments, fillers, preservativesand/or defoamers.
 8. A process for preparing a water-thinnable binder,characterized in that at least one polyacid/polyvinylpyrrolidone complexis added to a polymer dispersion prepared by emulsion polymerization andsubsequently, where appropriate, one or more water-soluble zirconiumcompounds, salts, acids, bases, low molecular mass organic substances,film formers, dispersants, protective colloids, stabilizers,surfactants, emulsifiers, polymers, thickeners, wetting agents,pigments, fillers, preservatives and/or defoamers are added to thepolymer dispersion/complex mixture.
 9. A water-thinnable coatingcomposition, characterized in that it comprises at least one binder ofat least one of claims 1 to
 7. 10. The water-thinnable coatingcomposition of claim 9, characterized in that it is a primer, exteriorpaint, interior paint, coating material, exterior render, interiorrender or coating composition for masonry constructions in the widestsense.
 11. A process for preparing a water-thinnable coatingcomposition, characterized in that the additives and/or auxiliariesnecessary for building up the coating composition are added to a binderof at least one of claims 1 to
 7. 12. A process for preparing awater-thinnable coating composition, characterized in that at least onebinder of at least one of claims 1 to 7 is added to a water-thinnablecoating composition.
 13. A process for preparing a water-thinnablecoating composition, characterized in that at least onepolyacid/polyvinylpyrrolidone complex and, where appropriate, one ormore water-soluble zirconium compounds are added to a water-thinnablecoating composition.
 14. Use of polyacid/polyvinylpyrrolidone complexesand mixtures comprising at least one polyacid/polyvinylpyrrolidonecomplex and, where appropriate, one or more water-soluble zirconiumcompounds in water-thinnable binders and coating compositions as dryingaccelerators.